Stabilizing High-Temperature α-Li3PS4 by Rapidly Heating the Glass.

High-temperature metastable phases exhibit superior characteristics compared to those of thermodynamically stable phases at room temperature. Although optimization of the compositions and crystallizations from glasses contribute to the stabilization of metastable phases at room temperature, the stabilization of the high-temperature α-Li3PS4 phase is not yet reported. α-Li3PS4 was successfully stabilized at room temperature, instead of the middle-temperature ß-Li3PS4 phase, via rapid heating to crystallize the Li3PS4 glass. The obtained electrolyte exhibited a high ionic conductivity of >10-3 S cm-1 at room temperature. The crystallization of the glass via rapid heating overcame the thermodynamic limitations in the preparation of the metastable crystals. Further development of materials via nonequilibrium states should contribute to the design of high-performance materials.

Stack Pressure Dependence of Li Stripping/Plating Performance in All-Solid-State Li Metal Cells Containing Sulfide Glass Electrolytes.

Sulfide-based all-solid-state Li/S batteries have attracted considerable attention as next-generation batteries with high energy density. However, their practical applications are limited by short-circuiting due to Li dendrite growth. One of the possible reasons for this phenomenon is the contact failure caused by void formation at the Li/solid electrolyte interface during Li stripping. Herein, we studied the operating conditions, such as stack pressure, operating temperature, and electrode composition, that could potentially suppress the formation of voids. Furthermore, we investigated the effects of these operating conditions on the Li stripping/plating performance of all-solid-state Li symmetric cells containing glass sulfide electrolytes with a reduction tolerance. As a result, symmetric cells with Li-Mg alloy electrodes instead of Li metal electrodes exhibited high cycling stability at current densities above 2.0 mA cm-2, a temperature of 60 °C, and stack pressures of 3-10 MPa. In addition, an all-solid-state Li/S cell with a Li-Mg alloy negative electrode operated stably for 50 cycles at a current density of 2.0 mA cm-2, stack pressure of 5 MPa, and temperature of 60 °C, while its measured capacity was close to a theoretical value. The obtained results provide guidelines for the construction of all-solid-state Li/S batteries that can reversibly operate at high current densities.

Formation of Passivate Interphases by Na3BS3-Glass Solid Electrolytes in All-Solid-State Sodium-Metal Batteries.

Interphase formation at the interface between a solid electrolyte and negative electrode is one of the main factors limiting the practical use of all-solid-state sodium batteries. Sulfide-type solid electrolytes with group 15 elements (P and Sb) exhibit high ductility and ionic conductivity, comparable to those of organic liquid electrolytes. However, the electronically conductive interphase formed at the interface between Na3PS4 and sodium metal increases the cell resistance and deteriorates its electrochemical properties. Contrarily, Na3BS3, containing boron as an electrochemically inert element, forms an electronically insulating thin passivate interphase, facilitating reversible sodium plating and stripping. Sodium-metal symmetric cells with Na3BS3 exhibit steady operation over 1000 cycles. Thus, reduction-stable solid electrolytes can be developed by substitution with an electrochemically inert element versus sodium.